Process for producing fast dyeings on the fiber



Patented Apr. 5, 1938 UNITED STATES PATENT oFF cE PROCESS FOR PRODUCING FAST DYEINGS ON THE FIBER Enrico Pool and Grald Bonhote, Base], and Carl Apotheker, Riehen, near Basel, Switzerland, assignors to firm of Society of Chemical Industry in Basie, Basel, Switzerland No Drawing. Application January I9, 1935, Se rial No. 2,602. In Switzerland January 27,

14 Claims.

amino-compound and then forming the azo-dye stuff by a suitable treatment. All these processes have the common feature that the diazo-compound or the product which contains the diazocompound ready made, such as the anti-diazotate or the diazo-amino-compound, is produced by treatment of the diazotizable base with nitrous acid not on the fiber but in a separate operation, in absence of the coupling component. It has not been possible-hitherto, without an essential impoverishment of the result in respect of depth and beauty of the coloring, to simplify the production of topical dyeings of azo-dyestuffs on the fiber by printing diazo-component and coupling component together on the fiber and then forming the dyestufi by causing nitrous acid to act on the mixture of coupling component or diazocomponent.

The present invention relates to a process in which the mixture consisting of a suitable (of not too low a melting point and little volatile) diazotizable amine, and alkali salt of a coupling component or a mixture of a coupling component and caustic alkali, and alkali nitrite is applied to the fiber and then, by passage of the fiber through acid, while avoiding high temperature (preferably at a temperature that does not exceed 25 0.), the amine is first diazotized and then, by a passage through an acid binding agent as a second operation the coupling is produced; in this manner dyeings are obtained which are incomparably finer than those obtainable by the hitherto'known methods on the fiber by diazotization of the diazo-component in the presence of the coupling component, and are equal not only to the dyeings obtained with the aid of preparations of ,diazo-amino-compounds or of nitro'samine, but also to those obtained by direct printing of the diazo-compound on the goods prepared with the coupling component. In many cases it may be of advantage, for the purpose of obtaining pure coloring, to add formaldehyde to the printing color. The invention owing to the simplicity of the process involves an important technical advance and could not be predicted from the available literature.

Among diazotizable amines having not too low a melting point are included such amines which do not melt much below 60 C. A great number of such bases is illustrated in the examples to follow. Among the diazotizing bases which come into consideration for the new process those are particularly useful which contain two aromatic nuclei linked by bridges, such as diaryl ethers, azo-compounds, monoacyl derivatives of aromatic diamines containing in the acyl radical an aromatic nucleus. Among the coupling components the arylides of hydroxycarboxylic acid are particularly valuable, and among these again the 2:3-hydroxynaphthoic acid and the 2:3hy-

droxyanthracene-carboxylic acid.

The production of the dyeings in accordance with the invention may be combined with the production of other dyestuffs, for example with that of aniline black, or effects produced by vatdyestufis or their leuco-sulfuric acid esters or the like.

The following examples illustrate the invention:

Example 1 A mixture is made from 331.2 parts by weight methoxy-l-aminobenzene, 232.2 parts of 2:3-hy- .doxynaphthoic acid-3'-nitranilide, 186 parts of sodium nitrite, 2 parts of sodium hydroxide and 69.1 parts of crystallized sodium acetate or the corresponding quantity of the anhydrous product. From this mixture there is prepared a finely subdivided printing color by carefully making a paste of 8 grams of the mixture, 38 cc. of water, 3 cc. of sodium hydroxide solution of 34 B., 3 cc. of Turkey red oil, 5 cc. of glycerin and 43 grams of neutral starch tragacanth thickening. The fabric, is printed .with this printing color, dried and quickly passed through an aqueous hydrochloric acid solution of 2 per cent. strength, containing 50 grams of sodium chloride per liter. The fabric is then wrung out and treated with an aqueous sodium carbonate, sodium bicar-' bonate or sodium acetate solution of 3-5 per cent. strength for a short time, whereby there is very quickly developed a fast, deep, pure violet color. The fabric is then rinsed and treated in a soap bath at the boil.

Example 2' v Amixture is made from, 240. 1parts by weight of b nzene-azo-ortho-anisidine, 288.9 parts of 2:3-hydroxynaphthoic acide 4' methoxyanilide, 245 parts of sodium nitrite, 24.2 parts of crystallized sodium acetate and 2 parts of sodium bydroxide. The printing color is then made from this mixture in the manner described in Example 1, and contains 80 grams of the mixture per kilo.

This printing color is printed, developed and after-treated as described in Example 1.

There is produced a deep, pure garnet-red dyeing. Similar tints are a-naphthalide or the Z-methoxyanilide is substituted for the 4'-methoxyanilide of 2:3-hydroxynaphthoic acid.

Example 3 296.4 parts by weight of 4-phenoxyacetylamin0-2:5-diethoxy-1-aminobenzene, 244.7 parts of 2 3-hydroxyanthracene-carboxylic acid-2'-methylanilide, 186 parts of sodium nitrite, 71 parts of crystallized sodium acetate and 2 parts of sodium hydroxide are mixed together. 8 grams of this mixture are made into a printing color in the manner described in Example 1. The goods are printed with the printing color, dried and passed through an aqueous solution of formic acid of 10 per cent. strength at ordinary temperature, then wrung out, suspended in air for 1 minute 'and treated with a sodium acetate solution of 5 per cent. strength for a short time at the room temperature; rinsing and soaping at the boil follow. There is obtained a pure green dyeing which is very fast.

Example 4 8 grams of a mixture consisting of 316.5 grams of 4- 2' -methyl) -phenoxyacetylamino-2 5-diethoxy-l-aminobenzene, 288.1 grams of 2:3-hydroxynaphthoic acid-3'-chloranilide, 190 grams of sodium nitrite, 2 grams of sodium hydroxide, 63 grams of crystallized sodium acetate are made into a paste with 36 cc. of water, 3 cc. of Turkey red oil, 5 cc. of glycerine, 3 cc. of sodium hydroxide solution of 34 B., 39 grams of neutral starch tragacanth thickening and 2 grams of sodium metanitrobenzene sulfonate. The goods are printed with this printing color and dried. There is further printed on the goods a vat-dyestuff in combination with a reducing agent and the goods are then passed through a rapid steamer and steamed for 3-5 minutes (fixation of the vatdyestufi) and finally developed and after-treated as described in Example 1. There areproduced deep blue efiects, besides those which are due to the vat-dyestufi used. Other blue prints are obtained, e. g., with the 4-phenoxyacetylamino- 2:5-diethcxy-1-aminobenzene and the metachloranilide of the 2:3-hydroxynaphthoic acid. There can also be used such phenoxyacetylamino-2:5-dialkoxy-l-aminobenzenes the alkoxy radicals of which contain more than two carbon atoms.

obtained when the sodium acetate.

Example 5 A printing color is prepared from 6 grams of p-naphthol, 6.5 grams of 4-amino-3:2'-dimethylazobenzene, 2.5 grams'of sodium nitrite, 5 cc. of sodium hydroxide solution of 34 B., 5.00. of Turkey red oil, 5 cc. of glycerine, 35 cc. of water and 37 grams of neutral starch tragacanth thickening. The goods are printed with this finely subdivided printing color, dried and then rapidly passed through an aqueous solution containing per liter 50 grams of sulfuric acid and 200 grams of Glaubers salt. The goods are now wrung out, hung in the air for a minute and treated at -70 C. with a sodium bicarbonate solution of 4 per cent. strength. Rinsing and soaping follow. There is obtained a Bordeaux red dyeing.

Example 6 273 parts by weight of 4:4'-dichloro-2-amino- 1:1-diphenylether are mixed with 264.3 parts of 2:3-hydroxynaphthoic acid-2'-methoxyanilide, 222 parts of sodium nitrite, 2 parts of sodium hydroxide and 38.3 parts of crystrallized The printing color is made-as f0llows:-

8 grams of the above mixture are very finely suspended in 3 cc. of sodium hydroxide solution of 34 B., 3 cc. of Turkey red oil, 37 cc. of water, 5 cc. of glycerine, 2 cc. of formaldehyde solution of 40 per cent. strength and 42 grams of neutral starch tragacanth thickening. The further procedure is as described in Example 1, but during the drying too high a temperature should preferably be avoided. There is obtained a pure red dyeing.

Example 7 pended in 3 cc. of sodium hydroxide solution of 1 34 B., 3 cc. of Turkey red oil, 37 cc. of water,

5 cc. of glycerine, 2 cc. of formaldehyde solution of 40 per cent. strength and 42 grams of neutral starch tragacanth' thickening. Further procedure is as described in Example 1, drying at too high a temperature being preferably avoided. There is obtained a pure red dyeing.

The following table shows a number of other dyeings which can be produced in accordance with this invention:-

Colo; ofttlie com ma 1011 Dino-component couplmgcomponent produced on cotton 4:4-dichloro-2-amlno-1:1'-diphm l m Di-(acetic acid)-orth9-ort ho-t9l idide Yellow- 2-amino-l-methyl-4-nitrobenzone- 2:3-hydroxynaphthoic acid-anilide a. Scarlet l-amlno-2-methyl-4-nitrobenune 2:3-hydroxy'naphthoic acid-2-methylaml1de Blue red 4-amino-3:2'-dimethyl-azobenzene 2:3-hydroxynaphthoic acid-anilide l-mnino-2-methoxy-5-chloro-4-benzoylaminobenzene. 1-amino-2-methoxy-5-methyl-4 benzoylamino benzene l-amino-2:5-dicthoxyA-benzoylaminobenzene. Pam-chlorophenyl-nzo-cresidine O-BnisOl-BtO-n-DB hthylaminc 1-amino-2-methy -4-nitrobenzcne 2:3hydroxynaphthoic acid-4-methoxy-a 2:3-hydroxynaphthoic acid-l'-naghthylamide 2:3-hydroxynaphthoic acid-anili e 2:3-hydroxynaphthoic acid-2-methoxyaml1d 2:3-hydroxynaphthoic acid-2'-naphthylamido.:.:

2:3-hydroxynaphthoicacid-anilide Violet 2:8-l1ydroxynaghthoic ncid-anilide Blue. 3-hydroxy-lr2- enzofluorenonc Black. 2:3-hydroxynaphthoic acid-anilide Violet black 2:3-hiydroXycarbazole-carboxylic ncid-parachlor- Brown.

an e 2:3-hydroxynaphthoic acid-4-ethoxy-anilidc Scarlet 2:3-hydroxynaphthoicacid-4-methoxy-amlide gag. e

Cole; of 1the com maion Diazo component Coupling component produced on cotton a-naphthylamine" 2:3-hydroxynaphthoicacid1-naphthy1amide; Bordeaux. 2-am no-5-acetyl-am1t c-4:4-dichloro-diphenylether. 2:3-hyd'r0xynaphthoic acid-4'-ethoxy-anllide Bordeaux red. 2-amino-4-aceto-4:4-dichloro-d1phenylether 2:3-hydroxynaphthoic acid-2-methoxy-anilide Red. 2-airl1lmo 5 acetylamino-4z4- dimethoxy-diphenyl- 2:3-l1ydroxynaphthoic acid4-methoxyanilide Violet,

0 er. nminoazob r 2:3-hydroxynaphthoic acid-anilide Bordeaux. 4-azn1no-2:E-dlmethyl-arobcnzene 2:3-hydroxynaphthoic acid-3-nitro-anilide Garnet. l-amino-2:5-dimcthoxy-4-benznylaminobenzene 2:3-hydroxynaphthoic acid-anilide Blue. 1-8mll10-2-ChlUlO'b'methOXy-4b0DZOylaminObeHZel16 2:3-hydroxvnaphthoic acid-2'-methoxy-anilide Currant. 4:4-dichloro-2-arnino-diphenylether 2:3i;gydroxycarbazole carboxylic acid-4-chlorani- Brown.

1 e. 4:4-dichloro-2amino-diphenylether di-(4-methyl-l-hydroxy-2-benzoyl)-dianisidide; Brown. l-amin0-2:S-diethoxy-l-benzoylaminobenzene 2-hydroxyanthracene Violet. l-amino-2-inethoxy-5-methyl-4- benzoylamiuoben- 2:8-hydroxynaphthalene-carboxylic acid-anilide. Red.

zene. l-arn'ino-2:5-diethoxy-l-benzoylaminobenzene 3:4-dimothyl-l-hydroxy-benzene- 6 c a r b 0 x yl ic Brown.

acid-2-naphthylamide. 4:4-dichloro-2-amino-diphenylether 3-chloro-4-methyl-l-hydroxy-benzene-6-carbox- Brown.

ylic acid 2-methyl-4-chloranilide. 2-amino-l:5-dimethyl-4-benzoylaminobeuzene 2:3-hydroxynaphthoic acid-2'-methoxy-auilide. Red.

The process-permits production of mixed tints by the use of suitable mixtures of parent material, whether of diazo-components or of coupling components, or both together.

vegetable textiles such as cotton, linen or ramie, further to artificial silk from regenerated cellulose, natural silk and the like.

What we claim is:

1. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing a solid diificultly volatile, diazotizable amine having a melting point not substantially below 60 C., a coupling component, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through r. dilute aqueous acid solution at a temperature not substantially in excess of 25 C. and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

2. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing a solid, dificultly volatile, diazotizable amine having a melting point not substantially below 60 C., an arylide of an aromatic ortho-hydroxy-carboxylic acid which couples with diazo compounds in ortho position to the OH group, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber Without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in exces of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

3. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing a solid, difiicultly volatile, diazotizable amine having a melting point not substantially below 60 C., an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution ata temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

4. A process for the production of fast tints on vegetable fiber which comprises printing the fiber It can be 7 applied to the most varying textiles, above all to r with a mixture containing a solid, difiicultly volatile, diazotizable amine having a melting point not substantially below 60 C. and comprising two aromatic nuclei linked by a N=N bridge, an arylide of 2:3 hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotiza tion of the amineon the fiber without coupling i 5. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing an orthoaminodiphenyl ether having a melting point not substantially below 60 C., an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C. and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

6. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing 4:4-dichloro-2- amino-diphenyl ether, an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling components by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

7. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing 4:4'-dichloro-2-aminodiphenyl ether, an ortho-anisidide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 0.; and then effecting the coupling of the diazotized amine and the coupling components by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

8. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing a mono-acidylated-. 1:4-diaminobenzene havinga melting point not substantialy below 60 C., an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the dia'zotization of the amine on the fiber without coupling by passing 'the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the coupling of I the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

9. A process for the production of fast tints on vegetable fiber which comprises printing the fiber diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C. and then eifecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acidbinding agent.

10. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing a mono-phenoxyacetyl 1:4 diamino 2:5-diethoxy-benzene, an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at .a temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

11. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a [mixture containing 4:2-methylphenoxyacet ylamino-1-amino-2 5-cliethoxy benzene, the m-chloranilide of 2:3-hydroxy-naphthoic acid, alkali and alkali metal nitrite; then effecting the dia'zotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the couplingof the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous soluon vegetable fiber which comprises printing the fiber with a mixture containing a monoaminomonoazo compound having a melting point not substantially below 60 C., an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then eifecting the diazotization of the amino on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

13. A process for the production offast tints on vegetable fiber which comprises printing the fiber with a mixture containing benzene-azaorthoanisidine, an arylide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

14. A process for the production of fast tints on vegetable fiber which comprises printing the fiber with a mixture containing benzene-azoorthoanisidine, an a-naphth'alide of 2:3-hydroxynaphthoic acid, alkali and alkali metal nitrite; then effecting the diazotization of the amine on the fiber without coupling by passing the printed fiber through a dilute aqueous acid solution at a temperature not substantially in excess of 25 C.; and then effecting the coupling of the diazotized amine and the coupling component by passing the treated fiber through a dilute aqueous solution of an acid-binding agent.

ENRICO POOL. GERALD BoNHTE. CARL APOTHEKER. 

